High temperature articles



March 1954 P. A. JENNINGS HIGH mmm ARTICLES Filed NOV. 14. 1950 Ill! 2% 35% N! UP TO 0.60%

FEI BALANCE INVEV NR.

NINGS PAU A. 9 4

HIS ATTORNEY Patented Mar. 9, 1954 2,671,728 HIGH TEMPERATURE ARTICLES ore,Md.,aslignorto ennings, Baltim Armco Steel Corporation; a corporation of Ohio- Application November 14, 1950, Serial No. 195,030

Claims. (0!. ii-128) This application is a continuation-in-part of my copending application Serial No. 141,291 filed January 30, 1950, now Patent 2,602,738, entitled High Temperature Articles, which application is a continuation-in-part of my then copending application, Serial No. 19,480 filed April 7, 1948, now Patent 2,495,731 of January 31, 1950, which is a continuation-in-part of my then copending application, serial No. 786,976 filed November 19, 1947, now abandoned, which in turn is a continuation-impart of my application Serial No. 762.863 flied July 23, 1947, also abandoned, and the invention relates to high temperature stainless steel articles. especially to articles in the form of valves, valve parts and other internal combustion engine components intended for use while hot in corrosive atmospheres.

Among the objects of my invention is the provision of strong, tough and durable austenitic stainless steel valves and other internal combustion engine components for elevated tempera-- ture use, which steel products. in view of the excellent properties of the particular steel employed function in a highly satisfactory manner in such fields as passenger car, truck. aircraft. diesel and marine vessel engine use. and which ofl'er great hardness at the high temperatures encountered in use, and substantial resistance, in the heated condition, to hot corrosive atmosposition, and-as high as"v pheres. such as those containing the combustion I products of anti-knock gasoline 'illustratively of the tetra-ethyl lead and lead bromide varieties.

Other objects of my invention in part will be obvious and in part pointed out more fully hereinafter.

The invention accordingly consists in the combination of elements, composition of materials and features of products, and in relation of each cfthesametooneormoreoftheothersas described herein. the scope of the application of which is indicated in the following claims.

Thesinglengureofthe= drawing represents a specific product and steel composition thcreof falling within the scope of my invention.

As conducive to a clearer understanding of certain features of my invention. it may be noted at this point that a great variety of heretofore known valves and valve parts intended for use as operating components of internal combustion engines or the like have become obsolete for such reasons as increased engine tempera tures incident to greater engine power and speed.

In average passenger cars. for example, the temll '2 peratures encountered by the valves frequently are as high as 700 F. or more'at, the fuel intake 1100' F. to 1450 F. or more at the exhaust position. These temperatures' ordinarily are .even higher in truck. bus. marine vessel or aircraftengines, especially in the region where the valves operate.

Low-alloy f valves, .forf esample, which formerly operated in internal combustion'engines'nbvg found in most instances to be unacceptablafl 'and so on the exhaust sideof theseengins. The valves usually burn or warp very quickly at the high operating temperatures, thus impairing engine eiilciency and requiring frequent replacement. While hot, the,working parts commonly develop oxide scale which detrimentally afiects proper seating. In turn, iailure of the valve to seat propertly allows leakage or blow-by of the hot gases. thus increasing the valve temperature and burning away the metal. An example of this type valve is one containing about 0.45% carbon, 8.50% chromium, 3.25% silicon. and the remainder substantially all iron.

Also. most of the low-alloy steel valves, including those having the composition lust noted, are extremely. susceptible to active corrosive attack by leaded fuels and particularly by the hot combustion products of these fuels. Thereare antilmock fuels containing lead on the market. which, when consumed, not only exert a ruinous eifect upon steel valves of low-alloy content, but a great majority of relatively high-alloy steel valvesand parts likewise suirer great detriment and rapid deterioration when exposed to the fuel combustion products.

A number of stainless steel valves, and valves made of other high-alloy metal, for example. have been introduced for better serving presentday needs. Some of these are of ferritic grade steel. Others are martensitic. In some, there is a high silicon content and. as a result, they enjoy adequate scaling resistance under certain ferritic or martensitic products. It is also true that the relatively high-alloy content of the chromium-nickel austenitic steel favors resists onges once to scaling from heat at -engine tempera tures. A further advantage often arising from austenitio steel valve products is their freedom from phase transformation and. in this respect.

freedom from volume changes and any resulting tendenciessuch as warpi s. sticking or cracking during the heating and coolingcycles brought about by the heat engine and its operation. The

- of lead oily-bromide as appears more fully hereinafter. Preferably the molybdenum content ranges from about 0.0% to 5.0%. I

On occasions. I use the element nitrogen in amounts up to about 0.30%, or even up to about 0.00%. as a substitute for an equivalent amount oi carbon or niokel in-the steel. The nitrogen 1 when used, serves the function of increasing the manyvaivescfthischaracterinthepriorart,-

however. leave much to be desired 'of resistance to corrosive attack by hot lead compounds.

An outstanding object of my invention, accordhots-hardness of the' steel. It also serves as a partial substitute tor other austenite-iorming elements to maintain the austenitic balance. Preferably my steel does contain nitrogen, and this ingly. is the provision of high temperature heatresistan t. corrosion-resistant stainless steel .valves. valve parts and internal combustion engine' components having substantial strength at the temperatures of use. which are substantially free of phase transformation, are hot hard, resist stretch. and eihciently and reliably resist oxiof my invention, I provide low-silicon. austenitic chromium-nickel-manganese stainless steel internal combustion engine valves, valve partaandanyorotherinternilcombustionem gins components made of the steel. illustratively Preferably, for desired hardness at the high temperatures encountered in actual use, the carbon content amounts to some 40% to 0.70%. The chromium content preferably ranges between 20.0% to 23.0% and the nickel content from 2.5% to 5.0%. By keeping an appreciable manganese content in the steel say 0.0% to 10.0%, and the silicon content below about 0.25%. I had sharp improvement in resistance or the steel products to corrosion and attack by products of combustion resulting from the burning of leaded fuel. At about 0.15% silicon and on down to 0.10% or less. this improvement is even more pronounced, and the hot-hardness is not adversely aifected. Both the hot-hardness and corrosion-resistance are even more favorable where the carbon exoeeds about 0.40% and the silicon ranges from about0.l5%ondownsubstantiallytoseroin amount. The smaller quantities of silicon accord- The inclusion of manganese and the preferred use of comparatively low nickel contents results flommydiscoverythatnickelinsteelsof the stainless grade often has an adverse eiIect upon the corrosion resistance of valve products while the latter operate in the presence of hot lead compounds. By supplanting a substantial quantity of the nickel ordinarily ing a steel of austenitic quality with manganese anausteniticbalancesteelishadandtheadtake or exhaust poppet valves, stems, heads, springs. casings. claddinss. linings or suri'acings.

in the ,amount of 0.15% to 0.50%.

Also. at times. I substitute the element cobal in discreet amounts for one or more or the austenite-io'rming' elements, nickel and f carbon.

required for providverseaifectofnickelmpon corrosionresistance,

in the combustionpmduets ofleaded fuels is importantly dispelled. Moreover. it seems that thesteeiofhighmanganesecon enthasagreah,

er solubility for carbon and as such permits sreaterhothardnessashighertemperaturesare Withthemolybdenumadditioninamountsof There are occasions too where my stainless steel products include in'the alloy composition thereof, as for special PW. oneor more such elements as titanium, columbium. tungsten. vanadium, copper, tantalum, aluminum, zirconium, or the like. rangingirom quite small amounts to substantial amounts not inconsistent with propertiesdesired.

m stainless valvesf valve parts as.. ginecomponents'whichI provide have a sulphur].

content which may quantity below about 0.04%. or even as much 0.2% or more. The

larger quantities of sulphur, and'especially those between about 0.15% to 0.20% contribute. to the effect of the low-silicon content in promoting resistance to attack by the combustion products of leaded gasolines and the like. The larger 'quantities of sulphur, say those beyond about 0.04%, usually improve the machining properties of the steel. Amounts of sulphur much beyond 0.00% often introduce hot working diiiiculties with certain or the austenitic steels which I employ; also, therateofhnprovementofresistancetolead oxide corrosion usually decreases for these greater amounts.- The phosphorus content of my products preferably is below about 0.04%.

The particular amounts oi such elements as chromium. nickel. molybdenum and manganese I present in the internal combustion engine products which I provide assure excellent heat resistance and resistance to oxidation at the high temperatures encountered. Also, the inclusion of manganese. and the restriction of silicon to the critically small amounts indicated. contribute to corrosion-resistance of the products in the combustion products of leaded fuels, as where the steel takes the form of an exhaust valve or part exposed to aircraft. truck or passenger car engine exhaust gases. By virtue of the austenitic quality of the steel. my valve products suifer substantially no phase transformation during heating and cooling cycles and, accordingly. are free of volume changes and difliculties often followinguponchangeofphase. 'I'hevalvesare 1''. and to lead cry-bromide at 1550' I for one 1.5% tol..0%1iindthatthesteeiacquires sub-- hour. and tenet-hardness tests at 1400' I". The

stsntiairesistanceto thccombustion produetsnresistanoetomoltentsadorldaandtheresist ance to lead oily-bromide,

.01 about 157 Brinellisgivenintermsot weight-loss in gramsper square decimeter per hour; and the hot-hardness in terms of Brineil coldball penetrato'r. All samples values using a are in the heat-treated condition, namely anhealing at 2150', F. for one hour and water quenched, ioilowed by age hardening at 1050' 1". ior 9 hours andw ter quenched.

' ram-n r titles oi nitrogen are introduced. the hardness substantially increases.i For example. with a nitrogen contents! about 0.22%. sample J, the hardness amounts to 185, and with 0.35%, sample K, it is 1,75. Nitrogen. therefore, clearly increases the hot-hardness'oi! my steel. and this without substantial sacrifice or the corrosion- -resisting properties.

influence of molybdenum on corrosion-resistance tomltenleadosideaad-tomoltsflieadonbromide of 21-4-9 chromium-Metamucil!- nese steel V Brlneil 0, Cr, in. ma.- Me, as; igg gam cent ercent percent percent percent percmt M15. 1W1 as r A .on 21.43 4.00 an .10 .00 19.45 less 145 4 13. .ea can us an .ss .10 sass 14.40 m 0. 1.50 11.00 4.0 0.00 a: .14 can 14.2: m n. .654 sass 4.0a an i. .14 race 1am in a. .cis use so: are r are .14 8.37 4.24 1eo r. .054 men 4.0: are not .is area 4.25 m O. 1.60 21.! 4.0 9.) I. .10 29.81 3.10 176 H- .026 20.82 3. 8.41 4.85 .17 81.08 2.0) ltd I .617 22 1.7! an it .10 race 180 I! Approshnatsoomposltlon.

The data presented above shows the important Thus it will be seen that in this invention eirect or the molybdenum addition,notonlyupon 80 there are provided low-silicon austenltic cmthe resistance or the steel to lead cry-bromide mlum- --moiybdenum stainless but on its hardness as well. Where the molybsteels and articles and products fashioned from exceeds about 1.8%, corrosion by sharply decreases. Minimum molybdenum content denum content lead cry-bromide corrosion is had where the is 2.0% or more.

The eilect at a purposeful nitrogen addition is demonstrated by the comparative figures given in Table II below. The samples analyse approximately 21% chromium, 4% nickel, 9% manganese. 2% molybdenum. 0.10% silicon, .60% carbon. with varying nitrogen contents and. remainder iron. All samples were heated at about 2150' F. ior one hour. then water-quenched and finally aged at a temperature of about 1350' F. for nine hours and water-quenched. The hot-hardness tests were made with a cold hall penetrator at 1400" F. and are reported in in molten lead compounds contained in a new magnesia crucible tor one hour. lead oxide at a temperature of 1675" F. in the one case and lead oxy-bromide at 1550' I". in the other. the weight loss being reported in grams per square decimeter.

TABLE II Influence sistance manganese-molybdenum steel the same in which the various objects noted hereinbelore together with many thorou hly successlully achieved. steels are well suited valve parts tion engine components, it will be understood that certain advantages of the invention are had irom other products of the low-silicon steel among which are high-temperature gas turbine nozzles, turbine parts adjacent to the nozzle, and any of a variety of supercharger components.

As many possible embodiments may be made oi my invention. and as many changes may be made in the embodiment hereinbeiore set iorth. it will be understood that all matter described herein is to be interpreted as illustrative and not as a limitation.

I claim 1. stainless steel having a 150 Brinell at a temperature or 1400' F.

and subof nitrogen on not-hardness and reto lead oxide of chromium-nickel- Mn, Mo,

percent percent percent Sample pcoent percent at W r-Nr' aa 8! 21. $5 551 ii. 18

see

one

I Approximate composition.

In Table II, it is noted that sample D, with nitrogen in the amount commonly lound in stainless steel (up to about 0.05%) has a hot-hardness Where substantial quanto corrosion in the resence products lead oxide containing about to 80% chromium.

stantial resistance of leaded fuel combustion and lead cry-bromide. and 75 0.08% to 1.50% carbon, 12%

7 2% to 85% nickel, 3% to 12% manganese, 1.5% to 0.0% molybdenum, up to 0.00% nitrog all in such proportions as to assure a substantially i'ully austenitic structure, silicon not exceeding 0.45%, and the remainder consisting essentially of iron.

2. Austenitie stainless steel having a hardness exceeding 150 Brinell at a temperature oi 1400' l".

- and substantial resistance to corrosion in the presence of leaded iuel combustion products lead oxide and lead cry-bromide, and containing about .495 to 1% carbon, 20% to 28% to 5% nickel, 8% to 12% manganese, 2% to 5% molybdenum, up to 0.6% nitrosen, silicon not exceeding 0.45%. and the remainder essentially of iron.

8. Austenitic stainless steel having a hardness exceeding 150 Brinell at a temperature or 1400' F.

-andsubstantiairesistancetocorrosloninthe praence oi leaded i'uel combustion products lead oxide and lead oily-bromide, and containing about 08% to 3% carbon, 20% to 23% chromium, 2.5% to 5% nickel, to 10% 2% to molybdenum, 0.15% to 0.50% nitrogen, silicon not exceeding 0.2231,. and the remainder consisting essentiallvoi 4, Allstenitie stainless steel having a hardness exceeding 150Brinell ate temperature or1400' I".

8 and substantial resistance to corrosion in the presence or leaded fuel combustion products lead oxide and lead oxy-bromide, and containing about .4% to 37% carbon, to 3% chromium,

5 2.5% to 5% nickel, 6% to 10% m,2% to 5% molybdenum, 0.04% to 0.20% sulphur, up to 0.60% nitrogen, silicon not exceeding 0.25%, and the remainder consisting essentially or iron.

5. Austenitic stainless steel internal tion engine exhaust valves resistant to lead oxi and lead city-bromide and having a hardness exceeding Brlnell at a temperature oi 1400 1''. comprising approximately .4% to .796 carbon. 2095 to 28% chromium, 2.5% to 5% nickel, 6% to 10% manganese, 2% to 5% molybdenum, up to 0.60% nitrogen, silicon not exceeding 0.25%, and the remainder consisting essentially o1 iron.

PAUL A. JENNINGS.

References Cited in the ille of this patent UNITED STATES PATENTS 

1. STAINLESS STEEL HAVING A HARDNESS EXCEEDING 150 BRINELL AT A TEMPERATURE OF 1400* F. AND SUBSTANTIAL RESISTANCE TO CORROSION IN THE PRESENCE OF LEADED FUEL COMBUSTION PRODUCTS LEAD OXIDE AND LEAD OXY-BROMIDE, AND CONTAINING ABOUT 0.08% TO 1.50% CARBON, 12% TO 30% CHROMIUM, 2% TO 35% NICKEL, 3% TO 12% MANGANESE, 1.5% TO 9.0% MOLYBDENUM, UP TO 0.60% NITROGEN, ALL IN SUCH PROPORTIONS AS TO ASSURE A SUBSTANTIALLY FULLY AUSTENITIC STRUCTURE, SILICON NOT EXCEEDING 0.45%, AND THE REMAINDER CONSISTING ESSENTIALLY OF IRON. 